Trialkanolamine derivatives



United States Patent 3,131,222 TRIALKANQLAMINE DERIVATIVES George M. Omietanski, Tonawanda, N.Y., assignor to The 9M0 State University Research Foundation, Columhus, Ohio No Drawing. Filed June 24, 1958, Ser. No. 744,085 5 Claims. (Cl. 260-584) This invention relates to quaternary nitrogenous salts. In one specific aspect, it relates to quaternized derivatives of substituted hydrazines. In still another aspect, it relates to novel tris(oxyalkyl)- and poly(oxyalkyl)hydrazinium salts and their metaloid derivatives.

Heretofore, quaternary hydrazinium salts have been obtained only on a laboratory scale. They have been prepared by the reaction of unsymmetrical dialkylhydrazines with alkylating agents, frequently lower alkyl halides. Because of the difiiculties involved in preparing the parent hydrazines, the uses of hydrazinium compounds have not yet been completely exploited. The present invention relates to a new class of heretofore unavailable hydrazinium compounds prepared by new synthetic methods capable of adaption to commercial production. This application is a continuation-in-part of my co-pending application Serial No. 582,657, filed May 4, 1956 and now abandoned which in turn is a continuation-in-part of my application Serial No. 544,091, filed October 31, i195 and now abandoned.

It is, therefore, an object of the present invention to provide a new generic class of tris(oxyalkyl)- and poly- (oxyalkyDhydrazinium compounds and their metaloid derivatives which, because of their unique structure and properties are useful intermediates for the synthesis of surfactant hydrazinium esters and the preparation of polymers which will not build-up electrostatic charges. These compounds, especially the borate and titanate esters, are useful as cross-linking or curing agents for certain ---classes f polymers, the most important of which are the epoxy resins." it 7 In accordance with the present inifiti'on I have made available a new generic class of useful hydrazinium compounds which may be represented as having the general formula:

(CnH2nO) x H NN(CnH nO) y M mA (011 211 In the above formula M may be H B or H,

OCnHQn CnHflnOH O C DH H2 When M is B or the aforementioned Ti containing substituent, x, y and z are integers having the value of l. When M is H x, y and z are integers having all Values between 1 and 20. Depending on the values of x, y and z, (C H O)x, C H O) and (C H O) are alkoxy or polyalkoxy groups wherein n is 2 or 3. The anion A is chloride or sulfate and m represents the number of anions required to balance the charge on the cation thus maintaining electrical neutrality of the salt. To express it in another fashion, the compounds of this invention comprise 1,1,1-tris-(2-hydroxyethyl)- and (2-hydroxypropyl)- I hydrazinium chloride and sulfate, their boron and titanium i chelates and their ethylene and propylene oxide condensates respectively.

My invention may be better described as compounds corresponding to the following general formulae:

In the above formulae x, y and z are integers having the values of 1 to 20; (C H O) (C I-1 0), and (C H O) represent alkoxy and poly alkoxy groups with n being 2. or 3. The charge on the anion A (chloride or sulfate) is p which also represents the number of cations required to maintain the electric neutrality of the salt.

The specific trialkanolamine derivatives of my invention can be prepared by several general methods and this discussion is not meant to be all inclusive. The preferred approach used here was the reaction of chloramine with suitable tertiary amines in accordance with the recent discovery that their reaction leads to the formation of 1,1,l-trisubstituted hydrazinium chlorides. Chloramine is readily available from the vapor phase reaction of chlorine and excess ammonia according to the process of Sisler et al., described in US. Patent No. 2,710,248. By treating that particular class of tertiary amines having a structure which is embraced by the general formula supra with chloramine, I am able to prepare the chloride salts of my novel hydrazinium compounds. In making the chloride compounds of the present invention, it is usually desirable to contact chloramine with a solution of the selected tertiary amine, allow the reaction to proceed until the desired quantity of chloramine is consumed and then isolate and purify the resultant hydrazinimum chloride by standard laboratory techniques. An excess of tertiary amine may be used in lieu of the inert solvent. While chloramine is most advantageously prepared in the form of a gaseous chlorarnine-ammonia stream obtained from a generator constructed according to the teachings of Sisler et 211., other methods are equally adaptable for the purposes of the present invention. For instance, chloramine caii'b'e made by reacting chlorine with an excess of ammonia in a halogenated hydrocarbon solvent under controlled conditions of mixing at low temperatures. Such a procedure is fully described in US. Patent No. 2,678,258 to John F. Haller. Another effective procedure is that of Coleman et al., described in detail in Inorganic Syntheses, vol. I, 59 (1939). Alternately the chloride compounds of the present invention can be made directly by the procedure described in the co-pending application of Bernard Rudner, Serial No. 605,230, filed August 20, 1956, now abandoned, which teaches the reaction of chlorine, ammonia and the tertiary amine in the presence of excess ammonia. For simplicity, when both the amine and the product are soluble in the same inert solvent, the Rudner method has been found to be a preferred technique.

As disclosed in my co-pending application Serial No. 696,949, filed November 18, 1957, now abandoned, hydroxylamine-o-sulfonic acid reacts with tertiary amines to form 1,1,1-trisubstituted hydrazinimum sulfates. That approach has been utilized to prepare the novel sulfate salts of this invention. Preferably the appropriate tertiary amine and hydroxylamine-o-sulfonic acid are allowed to react or are heated together in the presence of an alcoholic solvent but excess amine or other suitable solvents may be used. Even though the use of solvent is not required, superior results are obtained with a solvent because of the extremely exothermic reaction that quite often results. A frequent purification step is the treatment of the reaction mixture with a basic substance such as sodium carbonate to remove acidic constituents from the product hydrazinimum sulfate which is essentially neutral and stable to the action of base.

Further purification is Because of present in especially the sulfate salts, are quite often extremely hygroscopic and require careful drying in vacuo.

Amines suitable for the practice of my invention can be considered as and are in fact derivatives of ammonia. Treatment of ammonia with ethylene oxide gives triethanolamine; further reaction with ethylene oxide gives mixtures of higher oxyalkylated products. Propylene oxide and ammonia react in a similar propanolamine, etc. customarily, to a fixed epoxide-amine molar ratio.

fashion to give triisooxyalkylation is done But oxiranes are highly reactive and the reaction cannot be controlled to give the desired product exclusively. suits is a complex What actually remixture of the moiety 1,1,1-tris-(2- hydroxypolyalkoxyalk'yl)amine containing the average number of moles of alkylene oxide per mole of amine on long chain oxyalkylated constituents are de Such mixtures are not comnie of the number of moles The terminal hydroxyl reactive and can enter rcially ro- Resins based sirable in the art because of cheapness of cost, resistance to hydrolysis of the ether group and flexibility of the resin because of internal plasticization by the long chains present.

As is Well known, synthetic textiles, fibers, etc. normally have a great tendency to develop undesirable electrostatic charges. ium group,

Because of the positive charge on the hydrazinpolymers containing my novel compounds will not have the usual tendency to develop static electrical charges.

undergo reaction with chloramine and hydroxylamine-osulfonic acid to give the corresponding hydrazinium chlo ride and sulfate respectively.

Triethanolamine titanate and triisopropanolarnine titanate behave in a similar man In addition the,Jaydrazinium" spirotitanates may he-prepared'by the reaction of titanium tetrachloride with 1,1,1-tris-(2-hydroxyethyl) or 1 ,1,l-tris-(2-hydroxypropyl hydrazinium chloride. metaloid chelates,

My novel titanium and boron like the other compounds of my invention, are useful in polymer technology. Their special merit consists in their ability to cure epoxide resins at mild conditions.

Combination of the hydroxy groups in a metaloid chelate catalytically activates my novel compounds for reaction with epoxide well as with other condensation-capable groups.

The scope and utility of my invention is fu trated by the following examples: Example I groups particularly as rther illusmonia. A mixtures of chloramine,

process.

generator was constructed to prepare gaseous ammonia and nitrogen using this Such a gaseous chloramine-ammonia-nitrogen mixture was bubbled into a solution of 20 ml. (21.8 g.) of commercial triethanolamine in ml. of xylene for 68 minutes.

Use of a cold water bath was necessary to hold the reaction temperature below 45 C. Chloramine uptake was rapid and approximately of the chloramine in the reaction within five minutes after the gas 90% complete; all flask was consumed fiow had been stopped.

The white oil that precipitated during the reaction was separated by decantation, washed with hexane and carbon tetrachloride and Heating with limited quantities of then dried in a vacuum desiccator.

isopropyl alcohol gradually converted the oil to crystalline 1,1,1-tris-(2-hydroxyethyl)hydrazinium chloride, M.P.

The product was an extremely hygroscopic solid very soluble in water and ethyl alcohol and appreciably soluble in isopropyl alcohol but insoluble in hydrocarbon solvents. Aqueous solutions, when made alkaline, functioned as strong reducing media. Because of the reactivity of the terminal hydroxyl groups, acyl derivatives were readily formed.

Example II The gaseous chloramine mixture of Example I was passed into a solution of 200 g. of triethanolamine in 1000 ml. of chloroform. The gel-like product contained ammonium chloride and unreacted amine. Purification was accomplished by evaporating the entire reaction mixture to dryness, washing with ether, evaporating the residue after the addition of 50 ml. of 10% aqueous sodium carbonate and further washing with ether. The product was extracted by means of hot absolute alcohol. Evaporation of the solvent and drying in vacuo gave 220 g. of 1,1,l-tris-(2-hydroxyethyl)hydrazinium chloride as a pale yellow oil containing 16.6% chloride. Even though relatively pure, the product could not be made to crystallize. It was observed that once the crystalline product of Example I was exposed to moisture, it was converted to the same non-crystallizable viscous oil.

Example 111 tris-(2-hydroxyethyl)hydrazinium sulfate as an oil. The product was treated with sodium carbo nate flriem extracted with ethyLaleoholrF'ofifihg the extract into excess chloroform gave the product as a pale yellow hygroscopic oil.

Example IV The addition of 5.65 g. of hydroxylamine-o-sulfonic acid to 20 g. of triethanolamine without solvent generated much heat and resulted in a gummy precipitate of product and triethanolamine sulfate. The reaction mixture was worked up as in the previous example and with the same results.

Example V Still bottoms, the residue resulting from the manna facture and distillation of triethanolamine, is a dark viscous liquid mixture consisting mainly of N(C H O) H where according to the method of manufacture, X is usually less than 4 and averages from 1.5 to 3.5. Fifty g. of Still bottoms in 250 ml. of chloroform was treated with excess chloramine using the generator of Example I. The reaction mixture was filtered from ammonium chloride and the filtrate combined with isopropyl alcohol washings of the filter cake was evaporated free of solvent. The resultant thick dark oil was extracted with ether, made alkaline to phenolphthalein with 10% aqueous sodium carbonate, evaporated to dryness, rewashed with ether, taken up in isopropyl alcohol and poured into excess dioxane to yield a thick brown oil largely 1,1,l-tris-(2 hydroxypolyethoxyethyl)hydrazinium chloride. The product was purified by treatment of its aqueous solution with charcoal, filtration, evaporation of the water, solution in ispropyl alcohol and reprecipitation by addition to excess dioxane.

Example VI A mixture results having the general formula N(C H O) H(C H.;O) H(C H O) H in any batch the sums of x, y and 1 average 23 but may have values as low as 4 and as high as 50. A solution of 200 g. of the above oxyalkylated amine dissolved in chloroform was treated with excess chlorarnine by means of the aforedescribed generator. After separation of 26.5 g. of ammonium chloride, the filtrate was evaporated to a thick yellow oil which contained 6.9% unreacted amine and 3.14% ionic chloride. The product was extracted with ether till free of amine and then dried to a constant weight. There resulted 213 g. of 1,1,l-tri -(2 hydroxypolyethoxyethyl) hydrazinium chloride as a thick pale yellow oil containing 3.5% chloride (the theoretical value for x+y+x=23 is 3.4%).

Example VII The oxyalkylated amine of the previous example (51.5 g. dissolved in 50 ml. of methyl alcohol) was added to 5.6 g. of hydroxylamine-o-sulfonic acid in ml. of the same solvent. After refluxing for minutes, the solvent was allowed to evaporate. The resultant semicrystalline mass was treated with aqueous sodium carbonate, evaporated to dryness, extracted with ether, taken up in methyl alcohol, filtered and evaporated to dryness in vacuo to give the hydrazinium sulfate corresponding to the hydrazinium chloride of Example VI. The product was a hygroscopic, semi-crystalline, oil-white residue.

Example VIII A solution was prepared consisting of 25 ml. of a 41% solution of triethanolamine titanate,

Ti (OCH CH NCH CH OH] 2 in isopropyl alcohol and 25 ml. of dimethylformamide. A chloramine-ammonia gas stream was passed into this mixture at 2030 C. giving a strongly exothermic reaction. After all of the chloramine had been consumed, the reaction mixture was stirred into an excess of benzene. The chloramine adduct was subsequently sepamamnw and obtained in the form of an extremely viscous pastei lts"laboratory analysis was consistent with its formulation as the novel l,l-bis -(2-hydroxyethyl.)-1,1,1f,

1'-[spirotitan-bis-(2-oxyethyl)]dihydrazinium dichloride. Example IX Excess chloramine made as previously described was bubbled into a solution of 52 g. of triethanolamine titanate in 1000 ml. of 2-propanol. There resulted a mixed gel of the hygroscopic product and ammonium chloride. Evaporation of the filtrate in vacuo yielded the crude chlorarnine adduct of Example VIII to which the following structural formula is ascribed:

NC2H4OH C12 OHlOa N z The product was very sensitive to polymerization and hydrolysis and polymerized on attempted drying in vacuo.

6 Example X Chloramine as previously prepared was added to a solution of 33.7 g. of triethanolamine borate in chloroform. Filtration gave 44 g. of the combined solid prodnot and ammonium chloride. Solution in hot isopropyl alcohol followed by the addition of ethyl acetate allowed the ammonium chloride to be removed by filtration. Evaporation of the filtrate gave the product as a semisolid residue to which the formula has been ascribed.

Example XI When 5.65 g. of hydroxylamine-o-sulfonic acid in methanol was added to a solution containing 29 g. of triethanolamine titanate, an immediate gummy precipitate resulted which slowly dissolved on heating. On cooling a glass-like, oil-white solid was obtained which 2 had an analysis consistent with its being a polym erized bis hydrazinium sulfate (percent C=26.1, percent H=5.24, percent N=7.42, percent 8:825 and the percent ash as sulfate was 58.9%). The product was instantly hydrolyzed by water and readily polymerizable b h 25 I :l a im:

1. Compounds having the formula (01.11211 1H [HEN-N: (C H21; 0) yH:|A 30 (CuH2nO)Z D 4D ReferenesCited in the filelofthis patent UNITED STATES PATENTS 2,775,604 Zech Dec. 25, 1956 FOREIGN PATENTS 491,098 Canada Mar. 10, 1953 OTHER REFERENCES Audrieth et al.: J. Am. Chem. Soc., vol. 76, pp. 4869- 71 (1954).

Gever et al.: J. Org. Chem., vol. 14, pp. 813-816 (1949).

Singh: J. Chem. 800., vol. 103, pp. 604-13 (1913). Singh: J. Chem. Soc., vol. 105, pp. 1972-87 (1914). Omietanski et al.: J.A.C.S., 78 pp. 1211-13 (Mar. 20, 

1. COMPOUNDS HAVING THE FORMULA 